Borohydride Metallocene Complex of a Lanthanide, Catalytic System Including Said Complex, Polymerization Method Using Same and Ethylene/Butadiene Copolymer Obtained Using Said Method

ABSTRACT

The present invention relates to a borohydride metallocene complex of a lanthanide, to its process of preparation, to a catalytic system incorporating it, to a process for the copolymerization of olefins employing this catalytic system and to an ethylene/butadiene copolymer obtained by this process, the butadiene units of which comprise 1,2-cyclohexane or 1,2- and 1,4-cyclohexane links. 
     A complex according to the invention corresponds to one or other of the following formulae A and B: 
     
       
         
         
             
             
         
       
         
         
           
             where, in the formula A, two ligand molecules Cp 1  and Cp 2 , each composed of a fluorenyl group, are connected to the lanthanide Ln, such as Nd, and where, in the formula B, a ligand molecule, composed of two fluorenyl groups Cp 1  and Cp 2  which are connected to one another via a bridge P of formula MR 1 R 2 , where M is an element from group IVa, such as Si, and where R 1  and R 2 , which are identical or different, represent an alkyl group comprising from 1 to 20 carbon atoms, is connected to the lanthanide Ln, where L represents an alkali metal, such as Li, where N represents a molecule of a complexing solvent, such as THF, where x is an integral or non-integral number greater than 0 and where p is an integer equal to or greater than 1.

The present invention relates to a borohydride metallocene complex of a lanthanide, to its process of preparation, to a catalytic system incorporating this complex, to a process for the copolymerization of at least two olefinic monomers using this catalytic system and to a copolymer of ethylene and of butadiene obtained by this process, the units of which resulting from butadiene comprise 1,4-cyclohexane or 1,2-cyclohexane links.

It is known to use catalytic systems based on halogenated metallocene complexes of lanthanides for copolymerizing ethylene and a conjugated diene.

The document EP-A-1 092 731 teaches the use, in producing copolymers of ethylene and a conjugated diene, of a catalytic system comprising:

on the one hand, an organometallic complex represented by one of the following generic formulae A or B:

where Ln represents a lanthanide metal having an atomic number which can range from 57 to 71,

where X represents a halogen which can be chlorine, fluorine, bromine or iodine,

-   -   where Cp₁ and Cp₂ each comprise a cyclopentadienyl or fluorenyl         group which is substituted or unsubstituted and where P is a         bridge corresponding to the formula MR₁R₂, where M is an element         from Group IVa of the Periodic Table of the Elements and where         R₁ and R₂ represent an alkyl group comprising from 1 to 20         carbon atoms, and     -   on the other hand, a cocatalyst which is chosen from a group         consisting of an alkylmagnesium, alkyllithium, alkylaluminium,         and a Grignard reagent or which is composed of a mixture of         these constituents.

The document Patent WO-A-2004/035639 on behalf of the Applicants teaches the use, in producing copolymers of ethylene and butadiene, of a catalytic system comprising:

(i) a lanthanide metallocene complex represented by one or other of the following formulae:

where Ln represents a lanthanide metal having an atomic number which can range from 57 to 71,

where X represents a halogen which can be chlorine, fluorine, bromine or iodine,

where, in the first formula, two identical or different ligand molecules Cp₁ and Cp₂, each composed of a fluorenyl group which is substituted or unsubstituted, are connected to the said metal Ln, and

where, in the second formula, a ligand molecule composed of two identical or different fluorenyl groups Cp₁ and Cp₂ which are substituted or unsubstituted and which are connected to one another via a bridge P corresponding to the formula MR₁R₂, where M is an element from Group IVa of the Periodic Table of the Elements and where R₁ and R₂ represent an alkyl group comprising from 1 to 20 carbon atoms, is connected to the said metal Ln, and

(ii) a cocatalyst belonging to the group consisting of an alkylmagnesium, an alkyllithium, an alkylaluminium, and a Grignard reagent or which is composed of a mixture of these constituents.

Other catalytic systems based on monocyclopentadienyl complexes of lanthanide borohydride type are known in particular in the literature for the homopolymerization of diolefins.

Mention may be made, for example, of the paper by D. Barbier-Baudry, O. Blacque, A. Hafid, A. Nyassi, H. Sitzmann and M. Visseaux, European Journal of Inorganic Chemistry 2000, 2333-2336, which mentions a complex of formula (C₅H(iPr)₄)Ln(BH₄)₂(THF) including a monocyclopentadienyl ligand substituted by an isopropyl group (iPr), where THF is tetrahydrofuran, for the homopolymerization of isoprene or styrene after alkylation by a cocatalyst of organolithium type.

More recently, the paper by F. Bonnet, M. Visseaux, A. Pereira and D. Barbier-Baudry, Macromolecules, 2005, 38, 3162-3169, disclosed the use of a similar complex of formula (C₅Me₄(nPr))Nd(BH₄)₂(THF)₂ including a pentasubstituted monocyclopentadienyl ligand, where nPr is an n-propyl group, in the stereospecific 1,4-trans polymerization of isoprene after alkylation by a cocatalyst of dialkylmagnesium type.

It should be noted that these lanthanide borohydride monocyclopentadienyl complexes have not been used to date in the copolymerization of monoolefins and conjugated dienes.

The Chinese patent document 1 286 256 discloses, as polymerization catalysts for the synthesis of polymethacrylates, a borohydride metallocene complex of a lanthanide comprising a ligand molecule composed of a fluorenyl group corresponding to the following formula:

{[(X₁)₂(R₇)(C₅R₁R₂R₃R₄)(C₁₃H₆R₅R₆)]MX₂(L)_(n)}_(m), where:

X₁ represents an alkyl group having from 1 to 4 carbon atoms or a phenyl group,

X₂ represents Cl, BH₄, H, an alkyl group having from 1 to 4 carbon atoms, N[Si(CH₃)₃]₂, CH₂[Si(CH₃)₃] or tetrahydrofuran,

R₁, R₃ and R₄ represent H or the CH₃ radical,

R₂ represents H,

R₅ and R₆ represent H, an alkyl group having from 1 to 4 carbon atoms or Si(CH₃)₃,

R₇ represents Si, C, Ge or Sn,

M represents a lanthanide, yttrium or scandium,

L represents Si(CH₃)₃, Li(THF)₄, [crown ether Y] or [crown ether Y]-2,4-epoxyhexacycle,

n represents 0 or 1 and m=1 or 2 (if m=2, n=0),

Y is a monovalent metal.

Another recent research route has concerned borohydride metallocene complexes of lanthanides including a ligand based on two cyclopentadienyl groups. Mention may be made, for example, of the studies by S. M. Cendrowski-Guillaume et al., Organometallics, 2000, 19, 5654-5660, and Macromolecules, 2003, 36, 54-60, which have disclosed the use of such a metallocene complex, of formula (C₅Me₅)₂Sm(BH₄)(THF), where Me is a methyl group and where Sm is samarium, for specifically catalysing the polymerization of ε-caprolactone by ring opening.

Mention may also be made of the studies by M. Visseaux et al., Journal of Organometallic Chemistry, 691 (2006), pages 86-92, which have disclosed that the metallocene CP*₂Nd(BH₄)(THF), when it is used in combination with butylethylmagnesium, even in the presence of a large excess of THF, constitutes a very active catalyst for ethylene and, in the presence of a stoichiometric amount of butylethylmagnesium, makes possible the stereospecific 1,4-trans polymerization of isoprene.

To date, the copolymerization of olefins and conjugated dienes using borohydrate metallocene complexes of lanthanides has not been described and remains an objective to be achieved.

One aim of the present invention is to overcome this disadvantage and this aim is achieved in that the Applicants have just discovered, unexpectedly, that a novel borohydride metallocene complex of a lanthanide corresponding to one or other of the following two formulae A and B:

where Ln is a lanthanide having an atomic number of between 57 and 71 inclusive,

where, in the formula A, two identical or different ligand molecules Cp₁ and Cp₂, each composed of a fluorenyl group which is substituted or unsubstituted, are connected to Ln,

where, in the formula B, a ligand molecule composed of two identical or different fluorenyl groups Cp₁ and Cp₂ which are substituted or unsubstituted and which are connected to one another via a bridge P corresponding to the formula MR₁R₂, where M is an element from Group IVa of the Periodic Table of the Elements and where R₁ and R₂, which are identical or different, represent an alkyl group comprising from 1 to 20 carbon atoms, is connected to Ln,

where L represents an alkali metal chosen from the group consisting of lithium, sodium and potassium, where N represents a molecule of a complexing solvent, such as an ether, where x is an integral or non-integral number which is greater than 0 and where p is an integer which is equal to 1 or 2, can be used for the copolymerization of olefins and in particular for the copolymerization of monoolefins and conjugated dienes and more specifically still for producing, with a high catalytic activity, copolymers of ethylene and butadiene where the units resulting from the butadiene comprise 1,2-cyclohexane links.

It should be noted that this borohydride metallocene complex of a lanthanide according to the invention is, to the knowledge of the Applicants, the very first to date which makes possible the synthesis of a copolymer of at least one olefin and at least one conjugated diene comprising 1,2-cyclohexane links, when it is used in combination with an alkylation cocatalyst chosen from the group consisting of an alkylmagnesium, an alkyllithium, a Grignard reagent and a mixture of an alkyllithium and of an alkylaluminium.

As emerges from the above formulae A and B, it should be noted that this lanthanide metallocene complex according to the invention (also known as “lanthanidocene” by a person skilled in the art) specifically includes, on the one hand, two fluorenyl and borohydride groups connected to the lanthanide and, on the other hand, the alkali metal L, preferably lithium, associated with the molecule of complexing solvent N, which is preferably composed of tetrahydrofuran (THF).

Preferably, Cp₁ and Cp₂ are each composed of the same unsubstituted fluorenyl group which corresponds to the formula C₁₃H₉ or C₁₃H₈ for the formula A or B respectively.

Also preferably, these formulae A and B are such that x is equal to 1 and p is equal to 2, the complex according to the invention then being a dimer in both cases.

According to a particularly advantageous embodiment of the invention, the said complex corresponds specifically to the formula B, being in this case of type bridged via the bridge of formula MR₁R₂ in which the element M is preferably silicon and R₁ and R₂ are advantageously a methyl group.

More advantageously still, the said complex according to the invention corresponds to either of the formulae:

where Flu represents an unsubstituted fluorenyl group of formula C₁₃H₈ in the complex B′ or a fluorenyl group substituted by an alkyl group comprising from 1 to 20 carbon atoms in the group B″, where Me represents a methyl group, Si is silicon, Nd is neodymium, Li is lithium, Et₂O is an ether and x is an integer ranging from 0 to 3.

According to another advantageous characteristic of the invention, the said complex can be isolated in the form of single crystals, which makes it possible in particular to analyse it by the X-ray diffraction technique (see appended Annex 1) in order to obtain crystallographic data. More specifically, the Applicants have been able to establish that these single crystals of the complex B′ according to the invention are arranged according to a monoclinic lattice system.

The said complex according to the invention is advantageously obtained by a preparation process comprising the reaction of a ligand salt of formula P-Cp₁Cp₂-L₂ and of a lanthanide Ln tris(borohydride) dissolved in the said complexing solvent and of formula Ln(BH₄)₃N₃.

Preferably, in connection with the formula B′ according to the invention, the said ligand salt corresponds to the formula Me₂SiFlu₂-Li₂ and the said lanthanide tris(borohydride) corresponds to the formula Nd(BH₄)₃(THF)₃.

According to one embodiment of the invention, this preparation process comprises running, at ambient temperature, the said ligand salt, dissolved in another solvent, such as diethyl ether, onto the said solution of lanthanide tris(borohydride), in the form dissolved in this other solvent, stirring the solution at ambient temperature, filtering the stirred solution, concentrating the filtrate and/or drying the complex, and optionally adding a poor solvent to the concentrate in order to precipitate the complex.

A catalytic system according to the invention comprises, on the one hand, the said borohydride metallocene complex of a lanthanide as defined above and, on the other hand, the said cocatalyst chosen from the group consisting of an alkylmagnesium, an alkyllithium, a Grignard reagent and a mixture of an alkyllithium and of an alkylaluminium.

Advantageously, the said cocatalyst is butyloctylmagnesium.

As indicated above, this catalytic system according to the invention advantageously makes it possible to copolymerize several olefins, such as monoolefins and diolefins, which was not made possible by any catalytic system of the prior art based on a metallocene complex of lanthanide borohydride type.

It should also be noted that the said lanthanide borohydride metallocene complex confers, on the catalytic system according to the invention, a catalytic activity for the copolymerization of a monoolefin, such as ethylene, and a conjugated diene, such as butadiene, which is even higher than that provided by the halogenated metallocene complex of the abovementioned document WO-A-2004/035639 for the same copolymerization reaction.

A process for the copolynerization according to the invention of at least two olefinic monomers, such as a monoolefin and/or a diolefin, comprises a reaction of the said catalytic system in the presence of the said monomers and this reaction is preferably carried out in suspension or in solution in a hydrocarbon solvent, such as toluene, and at a temperature of between −20° C. and 120° C.

This reaction can be carried out under a variable pressure, preferably ranging from 1 bar to 50 bar, and, also preferably, at a temperature preferably of between 20° C. and 90° C.

The copolymerization process preferably comprises:

(i) the preliminary preparation of the said catalytic system outside the polymerization medium by reacting the said complex with the said cocatalyst, then

(ii) the reaction of the catalytic system obtained in (i) in the presence of the monomers to be polymerized.

In an alternative form, it should be noted, however, that the catalytic system might be formed in situ in the polymerization medium.

According to a particularly advantageous embodiment of the invention, this process comprises the copolymerization of ethylene and butadiene in order to obtain an ethylene/butadiene copolymer in which:

-   -   the molar level of units resulting from butadiene is         advantageously greater than 10% and more advantageously still         equal to or greater than 25%, and in which     -   the units resulting from butadiene comprise cyclic links in the         form of 1,2-cyclohexane, in addition to the usual trans-1,4 and         1,2(vinyl) links.

Advantageously, the molar level of the 1,2-cyclohexane links in the units of the said copolymer which result from butadiene is equal to or greater than 20% and more advantageously still equal to or greater than 25%. It should be noted that, in some cases, this level of 1,2-cyclohexane links can even be greater than 35%.

According to another characteristic of the invention, use is made of a cocatalyst/complex molar ratio of less than or equal to 10 and advantageously of less than or equal to 5, in order to obtain a number-average molecular weight Mn of the said copolymer which is equal to or greater than 50,000 g/mol.

More advantageously still, this cocatalyst/complex molar ratio is chosen to be less than or equal to 2 and the copolymerization is carried out under a pressure equal to or greater than 8 bar, for example equal to 10 bar, in order to obtain a number-average molecular weight Mn of the said copolymer which is equal to or greater than 200,000 g/mol.

A copolymer of ethylene and butadiene according to the invention which is capable of being obtained by the copolymerization process defined above advantageously exhibits both:

a) a molar level of units resulting from butadiene which is equal to or greater than 25%, and

b) a molar level of 1,2-cyclohexane links in the said units resulting from butadiene which is equal to or greater than 25%.

According to another characteristic of the invention, this copolymer of ethylene and butadiene exhibits, in addition to the two abovementioned characteristics a) and b), a number-average molecular weight Mn equal to or greater than 30,000 g/mol.

Advantageously, these copolymers according to the invention furthermore exhibit a polydispersity index PI which is less than 3.5 and more advantageously still less than or equal to 2.5. Following the example of the molecular weights Mn, the polydispersity indices PI were determined in the present description by steric exclusion chromatography (see the appended Annex 2).

The copolymers according to the invention preferably exhibit a glass transition temperature Tg which is less than −10° C. More specifically, these copolymers can, for example, exhibit a temperature Tg of between −20° C. and −50° C. This temperature Tg is measured in the present description by the Differential Scanning Calorimetry (DSC) technique. More specifically, these thermal analyses were carried out on a “Setaram 131” calorimeter. The samples were subjected to two rises in temperature from −100° C. to 100° C. at the rate of 10° C. min⁻¹. The data of the second rise in temperature were used to determine the thermal properties of the polymers.

The abovementioned characteristics of the present invention, and others, will be better understood on reading the following description of several exemplary embodiments of the invention, the said description being made with reference to the appended drawings, among which:

FIG. 1 illustrates the expanded chemical formula of a borohydride metallocene complex of a lanthanide according to the invention,

FIG. 2 illustrates the various links characterizing the insertion of the units resulting from butadiene into a copolymer of ethylene and butadiene prepared according to the invention by means of the complex of FIG. 1,

FIGS. 3 and 4 each illustrate the structure of the single crystals observed by X-ray diffraction which characterizes the complex according to the invention of FIG. 1,

FIG. 5 is a ¹H NMR spectrum relating to the complex according to the invention of FIG. 1 where only the high fields are represented (the signal relating to the BH₄ groups is not represented and appears at approximately 100 ppm),

FIG. 6 illustrates the expanded chemical formula of another lanthanide borohydride metallocene complex according to the invention,

FIGS. 7 and 8 each illustrate the structure of the single crystals observed by X-ray diffraction which characterizes the complex according to the invention of FIG. 6 (the carbon atoms of the ethers have been omitted from the representation for greater clarity).

For all the following examples, the procedure was carried out under argon and the solvents used were dried beforehand by a reaction with sodium, followed by distillation, or else over a 3 Å molecular sieve while flushing with argon.

All the metallocene complexes synthesised below were analysed by ¹H NMR in d₈-THF at a temperature of 22° C. using a “Bruker DRX 300” spectrometer at a frequency of 300 MHz and additionally, for the borohydride complex according to the invention, by the X-ray diffraction technique described in the appended Annex 1.

The microstructure of each copolymer obtained in these examples was determined by ¹H NMR and ¹³C NMR techniques. To this end, use is made of a “Bruker DRX 400” spectrometer at frequencies of 400 MHz for the ¹H NMR technique and of 100.6 MHz for the ¹³C NMR technique. The spectra were acquired using a 5 mm “QNP” probe at a temperature of 363 K. A tetrachloroethylene/perdeuterobenzene mixture (ratio by volume 2:1) was used as solvent.

1) Synthesis of a Complex 1 of Lanthanide Borohydride Metallocene Type According to the Invention of Formula [Me₂SiFlu₂Nd(BH₄)₂Li(THF)]₂

a) A salt of Me₂SiFlu₂Li₂ (Me and Flu respectively being a methyl group and an unsubstituted fluorenyl group) was synthesised as described in the document of Patent EP-A-1 092 731.

To this end, in a first step, a compound of formula Me₂Si(C₁₃H₉)₂ was synthesised. In order to do this, 18 mmol of C₁₃H₁₀ and 18 mmol of sodium hydride were stirred at reflux in THF overnight. 8.1 mmol of Cl₂SiMe₂ were subsequently added to this mixture and then the solution obtained was stirred at ambient temperature for 3 hours. A portion of the THF was subsequently evaporated and then heptane was added. The organic phase obtained was hydrolysed and was extracted several times with a saturated aqueous NH₄Cl solution. The solvent was then evaporated and, after drying the extract under vacuum at 60° C., the said compound of formula Me₂Si(C₁₃H₉)₂ was finally recovered.

4.4 mmol of this compound of formula Me₂Si(Cl₁₃H₉)₂ and 13 mmol of BuLi were subsequently stirred in toluene at ambient temperature overnight and then at 50° C. for 3 hours. The precipitate composed of a corresponding salt of formula Me₂SiFlu₂Li₂ was obtained and was washed with heptane and then dried under vacuum.

b) Furthermore, the neodymium borohydride of formula Nd(BH₄)₃(THF)₃ was synthesised as described in the paper by S. M. Cendrowski-Guillaume, G. Le Gland, M. Nierlich and M. Ephritikhine, Organometallics, 2000, 19, 5654-5660.

c) The complex 1 according to the invention was then synthesised in the following way.

515 mg (1.3 mmol) of the salt Me₂SiFlu₂Li₂, dissolved in 75 ml of diethyl ether, were run at ambient temperature onto a solution comprising 521 mg of Nd(BH₄)₃(THF)₃ (1.3 mmol) dissolved in 75 ml of diethyl ether.

The solution obtained was stirred at ambient temperature for 12 hours and filtered, and then the filtrate obtained was concentrated down to a total volume of 125 ml. 200 ml of pentane was subsequently run in with stirring. After the appearance of a diffuse cloudiness, stirring was halted.

Dark red crystals (360 mg, 0.56 mmol) formed after standing for 12 hours.

Thus, this reaction, at ambient temperature, resulted in the neodymium complex 1 according to the invention of molecular formula [Me₂SiFlu₂Nd(BH₄)₂Li(THF)]₂, the expanded formula being illustrated in FIG. 1. This complex 1 was isolated in the form of single crystals with a yield of 45%.

These single crystals of the complex 1 were characterized by X-ray diffraction and by ¹H NMR, as illustrated in FIGS. 3 and 4 and in the appended Annex 1, which shows in particular that these single crystals are arranged according to the monoclinic lattice system.

As emerges from the characterization by X-ray diffraction (FIG. 3 and FIG. 4), the complex 1 according to the invention of empirical formula [Me₂SiFlu₂Nd(BH₄)₂Li(THF)]₂ exists in the form of a dimer.

The molar mass M₁ of the dimer is equal to 1279.10 g.mol⁻¹. The ¹H NMR analysis confirms the structure of this complex 1 and the following assignment has been proposed for this complex 1:

(d₈-THF, 22° C.): 97.5 ppm, 8H, BH₄; 13.15 ppm, 6H, Si(CH₃)₂; 5 ppm, 4H, Flu; −2.35 ppm, 2*4H, Flu.

2) Synthesis of a “Control” Complex 2 of the Prior State of the Art of Lanthanide Halogenated Metallocene Type of Formula [Me₂SiFlu₂]NdCl

1090 mg (2.8 mmol) of Me₂SiFlu₂Li₂, dissolved in 50 ml of THF, were run at ambient temperature onto a solution comprising 620 mg (2.5 mmol) of NdCl₃ in 100 ml of THF (the NdCl₃ suspension was heated at reflux beforehand for 12 hours). The mixture was brought to reflux for 12 hours and then the solvent was evaporated. The product was extracted with toluene and a salt was removed by filtration. 1390 mg (2.4 mmol) of crude complex were obtained after evaporation of the filtrate, chloro(μ-dimethylsilyl)bis(η⁵-fluorenyl)neodymium of formula [Me₂SiFlu₂]NdCl and of molar mass M=566.27 g/mol.

This reaction required bringing the reaction medium to reflux and resulted in the complex 2 isolated in the form of a crude product. The X-ray diffraction analysis of this complex 2 was not possible as single crystals could not be obtained for this complex 2. Due to the paramagnetism of neodymium, no signal relating to the complex 2 could be observed by ¹H NMR, whether in d₈-THF or in d₅-pyridine.

3) Low-Pressure Copolymerization Tests (Starting Pressure=4 bar)

Each of these two complexes 1 and 2 was used in association with butyloctylmagnesium (abbreviated to “BOMAG”) as alkylating cocatalyst for the copolymerization of ethylene and butadiene. Each catalytic system 1 and 2 (respectively according to the invention and “control”) was prepared by carrying out a prior activation of the corresponding complex 1 or 2 by the cocatalyst “BOMAG” according to an Mg cocatalyst/Nd complex molar ratio varying from 1.9 to 10.4, the activation time being:

-   -   15 min for the tests 3-1, 3-2, 3-3 and 3-6,     -   12 h for the test 3-4, and     -   1 h for the test 3-5.

The polymerizations took place in a 250 ml glass reactor in 200 ml of toluene at a temperature of 80° C. and a starting pressure of 4 bar. The monomers were introduced into the medium in the form of a gas mixture comprising 30% of butadiene.

After a reaction time t (min), the copolymerization is halted by cooling and degassing the reactor and then the copolymer is obtained by precipitation from methanol. After drying, a weight w (g) of copolymer is obtained.

The results of the various tests are listed in Tables 1 to 3 below.

TABLE 1 Polymerization conditions Weight of Complex [Nd] in [Mg] in copolymer Time Tests Complex in mg μmol · l⁻¹ μmol · l⁻¹ [Mg]/[Nd] w in g in min 3-1 1 10.0 78 266 3.4 1.10 60 3-2 1 26.9 210 1064 5.1 11.00 180 3-3 1 13.1 102 1064 10.4 7.5 180 3-4 1 13.0 102 1064 10.4 7.8 180 3-5 1 27.7 217 418 1.9 12.6 180 3-6 2 (control) 33.0 194 388 2 8.50 240

TABLE 2 Activities of the complexes and macrostructure of the copolymers Activity in Activity in Mn Tg Tests g · mol⁻¹ · h⁻¹ g · g⁻¹ · h⁻¹ in g · mol⁻¹ PI in ° C. 3-1 70 500 110 50 800 2.59 −40.2 3-2 87 300 136 46 150 1.60 −36.0 3-3 122 550  191 33 300 1.68 −35.3 3-4 127 450  200 37 400 1.69 −37.1 3-5 96 800 152 74 850 1.54 −33.0 3-6 36 500 64 110 000  2.30 −37.0 (control)

where the columns expressed in g.mol⁻¹.h⁻¹ and in g.g⁻¹.h⁻¹ indicate the number of grams of copolymer obtained per mole (respectively per gram) of complex and per hour, thus constituting indicators of the catalytic activity of the complexes 1 and 2.

TABLE 3 ¹³C NMR characterization of the microstructure of the copolymers Molar % Molar % butadiene Molar % Molar % 1,2-cyclohexane Test units 1,4-trans links 1,2 links links 3-2 26.7 31.8 35.2 33.0 3-3 28.0 32.3 38.9 28.8 3-4 28.4 32.1 38.8 29.1 3-5 25.3 31.9 31.9 36.1 3-6 (control) 19.3 28.9 27.9 43.2

FIG. 2 is a schematic illustration of the various links observed for the insertion of butadiene units in the ethylene/butadiene copolymers thus prepared.

In the light of Table 2, it is apparent that the lanthanide borohydride metallocene complex 1 according to the invention, once alkylated by the cocatalyst, exhibits a much greater catalytic activity in g.g⁻¹.h⁻¹ than that of the “control” complex 2 which is at least substantially doubled, indeed even tripled (cf. tests 3-3 and 3-4), in comparison with that of this “control” complex of lanthanide halogenated metallocene type (cf. test 3-6).

In the light of Table 3, it is apparent that this complex 1 according to the invention makes it possible to obtain ethylene/butadiene copolymers in which the units resulting from butadiene are present according to a molar level of greater than 25% and always comprise 1,2-cyclohexane links, units resulting from butadiene, according to a relatively high molar level which is equal to or greater than 25%, indeed even 30%.

Thus, the test 34 according to the invention results in the production of a copolymer comprising 28.4% of units resulting from butadiene, including 29.1% of 1,2-cyclohexane links, with a catalytic activity of 200 g.g⁻¹.h⁻¹ for the complex 1 used, against only 64 g.g⁻¹.h⁻¹ for the “control” complex 2.

In addition, the test 3-5 according to the invention shows that it is possible to obtain a relatively high number-average molar mass Mn for the ethylene/butadiene copolymer (greater than 70 000 g/mol) by choosing a cocatalyst/complex molar ratio of less than 2.

4) High-Pressure Copolymerization Tests (Starting Pressure=10 bar)

Each of the two complexes 1 and 2 was used in association with “BOMAG” as alkylation cocatalyst and according to the same Mg cocatalyst/Nd complex molar ratio equal to 2 for the copolymerization of ethylene and butadiene. Each catalytic system 1 and 2 (respectively according to the invention and “control”) was prepared by carrying out a prior activation of the corresponding complex 1 or 2 by the cocatalyst “BOMAG” for a time of 15 min.

The polymerizations took place in a 1 litre metal reactor made of stainless steel, in 600 ml of toluene at 80° C. and at a starting pressure of 10 bar. The butadiene and ethylene monomers (respectively abbreviated to “Bd” and “E”) were introduced into the medium while varying the fraction of butadiene in the feed gas mixture.

The results of the various tests are listed in Tables 4 to 6 below.

TABLE 4 Polymerization conditions Weight of Complex [Nd] in E % Bd copolymer Polym. Tests Complex in mg μmol · l⁻¹ Bd in g in g Feed w in g time 4-1 1 33.3 87 8.1 24.95 14.4 25.6 1 h 00 4-2 1 34.0 88 22.6 24.35 32.5 31.7 2 h 45 4-3 2 (control) 22.0 65 8 □25 □14 5.9 3 h 00 4-4 2 (control) 47.2 138 18 □25 □30 15.8 2 h 20

TABLE 5 Activities of the complexes and macrostructure of the copolymers Activity in Activity in Mn in Tg Tests g · mol⁻¹ · h⁻¹ g · g⁻¹ · h⁻¹ g · mol⁻¹ PI in ° C. 4-1 492 300 769 297 000 3.16 −36.0 4-2 217 500 339 281 000 1.92 −45.6 4-3 (control)  50 400 89 378 600 2.8 −43.2 4-4 (control)  81 600 143  70 700 2.0 −45.7

where the columns expressed in g.mol⁻¹.h⁻¹ and in g.g⁻¹.h⁻¹ also indicate the number of grams of copolymer obtained per mole (respectively per gram) of complex and per hour, thus constituting indicators of the catalytic activity of the complexes 1 and 2.

TABLE 6 ¹H NMR characterization of the microstructure of the copolymers Molar % Molar % Molar % 1,2- Molar % Bd in 1,4-trans Molar % cyclohexane Tests Bd in feed copolymer links 1,2 links links 4-1 14.4 12.9 25.3 39.6 35.1 4-2 32.5 30.8 29.6 50.3 20.2 4-3 □14 20 26.7 44.5 28.8 (control) 4-4 □30 30.4 27.8 53.5 18.7 (control)

In light of Table 5, it is apparent that the lanthanide borohydride metallocene complex 1 according to the invention, once alkylated by the cocatalyst, exhibits a much greater catalytic activity in g.g⁻¹.h⁻¹ than that of the “control” complex 2 which is more than doubled, indeed even more than quadrupled (cf. tests 4-1 and 4-2), in comparison with that of this “control” complex of lanthanide halogenated metallocene type (cf. tests 4-3 and 4-4).

In light of Table 6, it is apparent that this complex 1 according to the invention makes it possible to obtain ethylene/butadiene copolymers in which the units resulting from butadiene are present according to a molar level of greater than 10%, indeed even 30%, and always comprise 1,2-cyclohexane links according to a relatively high molar level which is greater than 20%, indeed even 30%.

Thus, the test 4-2 according to the invention results in the production of a copolymer comprising 30.8% of the units resulting from butadiene, including 20.2% of 1,2-cyclohexane links, with a catalytic activity of 339 g.g⁻¹.h⁻¹ for the complex 1 used, against only 143 g.g⁻¹.h⁻¹ for the “control” complex 2 tested in the test 4-4, carried out under polymerization conditions similar to those of the test 4-2, as a result of a butadiene feed of approximately 30% (cf. Table 4).

It should also be noted that these high-pressure (10 bar) polymerizations, which are associated with a reduced Mg cocatalyst/Nd complex molar ratio (equal to 2), allow the complex 1 of the invention to confer, on the copolymer obtained in the test 4-2, a much greater molar mass Mn (greater than 281 000 g/mol) than that provided by the “control” complex 2 (70 700 g/mol) under the similar conditions of the test 4-4.

In conclusion, the lanthanide borohydride metallocene complex 1 according to the invention makes it possible to prepare copolymers of ethylene and butadiene exhibiting 1,2-cyclohexane units with very high catalytic activities which are the highest known to date to the knowledge of the Applicants.

5) Low-Pressure Homopolymerization Test (Starting Pressure=4 bar)

Use was made of the complex 1 in association with butyloctylmagnesium (abbreviated to “BOMAG”) as alkylating cocatalyst for the polymerization of ethylene. The catalytic system according to the invention was prepared by carrying out a prior activation of the complex 1 by the cocatalyst “BOMAG” according to an Mg cocatalyst/Nd complex molar ratio of 10.4, the activation time being 15 min.

The polymerization took place in a 250 ml glass reactor, in 200 ml of toluene at a temperature of 80° C. and at a pressure of 4 bar.

After reacting for 25 minutes, the polymerization is halted by cooling and degassing the reactor and then the polymer is obtained by precipitating from methanol. After drying, 7.1 g of polyethylene, having an Mn=7700 g.mol⁻¹ and a polydispersity index PI=1.98, are obtained.

Weight of Time Complex [Nd] [Mg] in homopolymer in Test Complex in mg μmol · l⁻¹ μmol · l⁻¹ [Mg]/[Nd] w in g min 5-1 1 13.1 102 1065 10.4 7.1 25

The lanthanide borohydride metallocene complex 1 according to the invention, once alkylated by the cocatalyst, exhibits a catalytic activity in g.mol⁻¹.h⁻¹ of 831 900.

6) Synthesis of a Complex 3 of Lanthanide Borohydride Metallocene Type According to the Invention of Formula Me₂SiFlu′₂Nd(BH₄)₂Li(ether)₃ (Flu′=2,7-^(t)Bu₂C₁₃H₆)

a) A salt of formula [Me₂SiFlu′₂]Li₂(THF)₂ was synthesised (Me and Flu′ respectively being a methyl group and the 2,7-di(tert-butylfluorenyl ligand).

To this end, in a first step, a compound of formula [2,7-^(t)Bu₂C₁₃H₇][Li] was synthesised. 17.8 ml of a BuLi solution (1.6M, 28.4 mmol) were run onto a solution of 2,7-^(t)Bu₂C₁₃H₈ (7.54 g, 27.1 mmol) in toluene (50 ml). The mixture was stirred at ambient temperature for 15 hours and then brought to 60° C. for 2 hours. The salt which precipitates is recovered by filtration. [2,7-^(t)Bu₂C₁₃H₇][Li] is subsequently washed with heptane and then dried under vacuum (5.88 g, 76%).

3.64 g of [2,7-^(t)Bu₂C₁₃H₇][Li] (12.8 mmol) are dissolved in THF (150 ml). The solution is cooled to −50° C. and then SiMe₂Cl₂ is added (6.4 mmol). The mixture is brought back to ambient temperature and is then stirred for 15 hours. The THF is evaporated and then the product is extracted with 50 ml of toluene. The solvent is evaporated to give a beige solid of formula Me₂Si(2,7-^(t)Bu₂C₁₃H₇)₂. The compound Me₂Si(2,7-^(t)Bu₂C₁₃H₇)₂ is subsequently dissolved in 50 ml of THF. The solution is cooled to 0° C. and then 8.0 ml of a BuLi solution (1.6M, 12.8 mmol) are added. The mixture is brought back to ambient temperature and is then stirred for 15 hours. The THF is evaporated and the product is washed with cold heptane. 4.8 g of dilithium salt [Me₂Si(2,7-^(t)Bu₂C₁₃H₆)₂]Li₂(THF)₂ are obtained (97%).

The product was characterized by proton NMR and its molecular formula is: [Me₂Si(2,7-^(t)Bu₂C₁₃H₆)₂]Li₂(THF)₂ (MW=769.10 g.mol⁻¹).

The assignments are:

¹H NMR (d₈-THF, 22° C.): 0.96 ppm (s, 6H, SiMe₂); 1.39 ppm (s, 36H, t-Bu); 1.78 and 3.62 ppm (m, 2*8H, 2*THF); 6.65 ppm (d, J=8 Hz, 4H, FluH); 7.78 ppm (d, J=8 Hz, 4H, FluH); 8.02 ppm (s, 4H, FluH).

b) Furthermore, the neodymium borohydride of formula Nd(BH₄)₃(THF)₃ was synthesised as described in the paper by S. M. Cendrowski-Guillaume, G. Le Gland, M. Nierlich and M. Ephritikhine, Organometallics, 2000, 19, 5654-5660.

c) The compound 3 according to the invention was then synthesised in the following way:

The salt [Me₂Si(2,7-^(t)Bu₂C₁₃H₆)₂]Li₂(THF)₂ (6.4 mmol), dissolved in 75 ml of THF, was run at ambient temperature onto a solution comprising 2.59 g (6.4 mmol) of Nd(BH₄)₃(THF)₃ dissolved in 75 ml of THF. The mixture is kept stirred for 15 hours and then the solvent is evaporated. A residue which is red-brown in colour is obtained. Diethyl ether (175 ml) is subsequently added. The solution obtained is filtered and then the filtrate is concentrated down to a total volume of approximately 75 ml (appearance of cloudiness). 75 ml of pentane are then added with stirring. Stirring is halted and the solution is left standing. Crystals are formed, along with an oil. The supernatant is removed and lengthy drying is carried out under vacuum. A solid residue mixed with crystals is obtained (2.45 g).

Thus, this reaction at ambient temperature resulted in the neodymium complex 3 according to the invention of molecular formula [Me₂Si(Flu′)₂Nd(BH₄)₂Li(ether)₃], the expanded formula being illustrated in FIG. 6.

The single crystals of the complex 3 were characterized by X-ray diffraction, as illustrated in FIGS. 7 and 8, which show in particular that the crystals are arranged according to the triclinic lattice system. The complex 3 according to the invention furthermore exists in the monomeric form and the unit cell comprises two crystallographically independent complexes.

Its molar mass M₃ is between 1008 and 1012 g.mol⁻¹ depending on whether the ether molecules of the structure are THF, diethyl ether or a mixture of the two.

7) Low-Pressure Copolymerization Tests

Use was made of the complex 3 in association with butyloctylmagnesium (abbreviated to “BOMAG”) as alkylation cocatalyst for the copolymerization of ethylene and butadiene. Each catalytic system 3 was prepared by carrying out a prior activation of the complex 3 by the cocatalyst “BOMAG” according to an Mg cocatalyst/Nd complex molar ratio equal to 5, the activation time being 15 min for all the tests 7-1 to 7-5.

The polymerizations took place in a 250 ml glass reactor, in 200 ml of toluene at a temperature of 80° C. and at a starting pressure of 4 bar or 2 bar in the case of the test 6-5. The monomers were introduced into the medium in the form of gas mixtures comprising 10, 20 and 30% of butadiene.

After a reaction time t (min), the polymerization is halted by cooling and degassing the reactor and then the copolymer is obtained by precipitation from methanol. After drying, a weight w (g) of polymer is obtained.

TABLE 7 Polymerization conditions (complex 3) Weight of Complex [Complex] [Mg] in Final p copolymer Polym. Tests in mg in μmol · l⁻¹ μmol · l⁻¹ % Bd feed in bar w in g time 7-1 50.0 247 1235 30 2.8 7.61 4 h 00 7-2 49.6 246 1230 30 2.7 7.66 4 h 00 7-3 54.4 269 1345 20 4 9.74 2 h 10 7-4 51.8 256 1280 10 4 9.19 1 h 40 7-5 55.0 272 1370 10 2 8.90 6 h 20

TABLE 8 Activities of the complex 3 and macrostructure of the copolymers Activity in Activity in Mn in Tests g · mol⁻¹ · h⁻¹ g · g⁻¹ · h⁻¹ g · mol⁻¹ PI Tg in ° C. 7-1 38 400 38 31 600 1.69 −28.3 7-2 38 900 39 29 550 1.50 −28.2 7-3 83 300 82 26 950 1.52 −35.7 7-4 107 300  106 11 885 1.65 −33.6 7-5 25 750 26  1 600 1.56 —

TABLE 9 ¹³C NMR characterization of the microstructure of the copolymers Molar % Molar % Mol. % Mol. % Mol. % Mol. % Bd units Bd units in 1,4-trans Mol. % T-1,2- C-1,2-Cy 1,4-Cy Tests in feed copolymer links 1,2 links Cy links links links 7-1 30 32.1 21.5 57.5 19.0 1.9 * 7-3 20 21.6 19.2 32.8 34.3 4.2  9.6 7-4 10 12.8 17.5 20.2 41.9 5.5 14.7 7-5 10 10.2 25.4 7.6 45.9 5.2 15.9 * The 1,4-αCy signal could not be integrated due to its low intensity and the superimposition of new small signals. It can be estimated that the level of the 1,4-cyclohexane units represents less than 5% of the butadiene units inserted. In Table 9: T-1,2-Cy means trans-1,2-cyclohexane units in the copolymer chain C-1,2-Cy means cis-1,2-cyclohexane units in the copolymer chain 1,4-Cy means 1,4-cyclohexane units in the copolymer chain.

The copolymer obtained using the complex 3 exhibits units resulting from butadiene comprising links in the form of 1,4-cyclohexane and 1,2-cyclohexane.

Annex 1 Analysis of the Lanthanide Borohydride Metallocene Complex According to the Invention by the X-Ray Diffraction Technique

The analysis by X-ray diffraction was carried out on a diffractometer using an MoKα source provided with a graphite monochromator (wavelength equal to 0.71069 Å) at a temperature of 150 K.

The crystals of the sample were transferred, in a glovebox under an argon atmosphere, into a small petri dish and covered with Paratone-N (Hampton Research). A small fragment was subsequently cut out and analysed using a “KappaCCD” diffractometer from “Bruker AXS”. The intensities diffracted were measured at 150 K with the “Collect” software with Φ and ω scanning at the K□ wavelength of molybdenum. The images obtained were integrated and the intensities were scaled with the “Denzo-SMN” program package.

The structure was resolved by direct methods:

-   -   with the “SIR97” program, cf. the paper by A. Altomare, M. C.         Burla, M. Camalli, G. Cascarano, C. Giacovazzo, A.         Guagliardi, A. G. G. Molitemi, G. Polidori and R. Spagna,         “SIR97, An integrated package of computer programs for the         solution and refinement of crystal structures using single         crystal data”, and     -   by least-squares refinement, with the “SHELXL” program, cf. the         paper by G. M. Sheldrick: SHELXL-97, Universität Göttingen,         Göttingen, Germany, 1997.

The crystallographic data are summarized in the following table.

Crystallographic Data of the Lanthanide Borohydride Metallocene Complex 1

Molecular formula C₃₂H₃₈B₂LiNdOSi Molecular weight 639.51 g/mol Crystal faces Orange block Dimensions of the crystals (mm) 0.22 × 0.22 × 0.18 Crystal system Monoclinic Space group P2₁/c a(Å) 10.4230(10) b(Å) 14.5290(10) c(Å) 19.5760(10) α(°) 90.00 β(°) 100.8500(10) γ(°) 90.00 V(ÅP^(3P)) 2911.5(4) Z 4 d(g-cmP^(−3P)) 1.459 F(000) 1300 μ(cmP^(−1P)) 1.848 Absorption corrections Multiscanning; 0.6866 min, 0.7321 max Diffractometer used “KappaCCD” X-ray source MoKα λ(Å) 0.71069 Monochromator Graphite T(K) 150.0(1) Scanning mode Phi and omega scans θ maximum 30.02 “HKL” ranges −14 14; −18 20; −27 27 Reflections measured 13551 Unique data 8443 “Rint” 0.0192 Reflections used 6770 Criterion I > 2σI) Type of refinement Fsqd Hydrogen atoms Mixtures Refined parameters 373 Reflections/parameters 18 wR2 0.0841 R1 0.0317 Weights a, b 0.0454; 0.0000 GoF 1.033 Difference peak/hole (e ÅP^(−3P)) 1.747(0.094)/−0.901(0.094)

Annex 2 Analysis by Steric Exclusion Chromatography of the Copolymers

a) For the copolymers which are soluble at ambient temperature in tetrahydrofuran (THF), the molar masses were determined by steric exclusion chromatography in THF. The samples were injected using a “Waters 717” injector and a “Waters 515 HPLC” pump at a flow rate of 1 ml.min⁻¹ into a series of “Polymer Laboratories” columns.

This series of columns, placed in a chamber thermostatically controlled at 45° C.1, is composed of:

-   -   1 precolumn: PL Gel 5 μm,     -   2 columns: PL Gel 5 μm Mixed C,     -   1 column: PL Gel 5 μm 500 Å.

Detection was carried out using a “Waters 410” refractometer.

The molar masses were determined by relative calibration using polystyrene standards certified by “Polymer Laboratories”.

Without being an absolute method, SEC makes it possible to understand the distribution of the molecular weights of a polymer. Starting from commercial products which are standards, the different number-average molecular weights (Mn) and weight-average molecular weights (Mw) can be determined and the polydispersity index calculated (PI=Mw/Mn).

b) For the copolymers which are insoluble at ambient temperature in tetrahydrofuran, the molar masses were determined in 1,2,4-trichlorobenzene. They were first of all dissolved under hot conditions (4 h 00 at 150° C.) and were then injected at 150° C. with a flow rate of 1 ml.min⁻¹ into a “Waters Alliance GPCV 2000” chromatograph equipped with three “Styragel” columns (2 “HT6E” columns and 1 “HT2” column).

Detection was carried out using a “Waters” refractometer.

The molar masses were determined by relative calibration using polystyrene standards certified by “Polymer Laboratories”.

Annex 3 ¹H and ¹³C NMR Determination of the Microstructure of the Butadiene Units Inserted into the Copolymers of Ethylene and Butadiene

High-resolution NMR spectroscopic analysis was carried out with a Bruker DRX 400 spectrometer at frequencies of 400 MHz for observation of ¹H and 100.6 MHz for observation of ¹³C. The 1D spectra were obtained with a 5-mm QNP probe at a temperature of 363 K. For the 2D spectra, use was made of a broadband probe with a field gradient along the z axis. The ¹H-¹H correlations were determined with a COSY-GS sequence and the ¹H-¹³C correlations with the HMQC-GS and HMBC-GS sequences. A mixture of tetrachloroethylene (TCE) and perdeuterobenzene (C6D6) (ratio 2/1 by volume) was used as solvent. The concentrations of polymer for the analysis are between 10 and 15% (w/w). The chemical shifts (δ) are given in ppm using tetramethylsilane (TMS) as internal reference; in the absence of TMS, the resonance of polyethylene (“PE” at δ=30.06 ppm) is used as internal reference.

Notations

The following symbols have been used in all the schemes and tables of this annex:

T: butadiene or isoprene unit inserted as trans-1,4,

C: butadiene or isoprene unit inserted as cis-1,4,

L: butadiene unit inserted as cis- or trans-1,4,

V: butadiene unit inserted as 1,2(vinyl),

E: ethylene unit,

B: butadiene unit (without distinction in microstructure),

T-1,2-Cy: trans-1,2-cyclohexane unit,

C-1,2-Cy: cis-1,2-cyclohexane unit,

1,4-Cy: 1,4-cyclohexane unit.

As concerns the assignment of the signals resulting from the 1,2 (V) and trans-1,4 (T) butadiene units and the trans-1,2-cyclohexane (T-1,2-Cy) units, reference should be made to the paper “Investigation of Ethylene/Butadiene Copolymers Microstructure by ¹H and ¹³C NMR”: M. F. Llauro, C. Monnet, F. Barbotin, V. Monteil, R. Spitz, C. Boisson, Macromolecules, 2001, 34, 6304.

TABLE 1 Chemical shifts of the carbons relating to the trans-1,2-cyclohexane units Type of carbon δ (ppm) T-1,2-αCy 33.96 T-1,2-βCy 27.00 T-1,2-γCy 30.59 T-1,2-α′Cy 32.26 T-1,2-β′Cy 26.66 T-1,2-(CH)Cy 42.01

TABLE 2 Chemical shifts of the carbons relating to the cis-1,2-cyclohexane units Type of carbon δ (ppm) C-1,2-αCy 28.14 C-1,2-βCy 29.25 C-1,2-γCy C-1,2-α′Cy 30.50 C-1,2-β′Cy 24.22 C-1,2-(CH)Cy 39.67

TABLE 3 Chemical shifts of the carbons relating to the 1,4-cyclohexane units Type of carbon δ (ppm) 1,4-αCy 37.90 1,4-βCy 27.30 1,4-γCy 30.40 1,4-α′Cy 33.90 1,4-(CH)Cy 38.40

Crystallographic Data of the Complex 3

Molecular formula C₅₆H₈₆B₂LiNdO₃Si Molecular weight 1008.18 g/mol Crystal faces Yellow block Dimensions of the crystals 0.20 × 0.18 × 0.15 (mm) Crystal system Triclinic Space group P-1 a(Å) 16.5340(10) b(Å) 18.0490(10) c(Å) 21.2150(10) α(°) 75.0600(10) β(°) 71.0500(10) γ(°) 71.2000(10) V(ÅP^(3P)) 5584.9(5) Z 4 d(g-cmP^(−3P)) 1.189 F(000) 2100 μ(cmP^(−1P)) 0.990 Absorption corrections Multiscanning; 0.8267 min, 0.8658 max Diffractometer used KappaCCD X-ray source MoKα λ(Å) 0.71069 Monochromator Graphite T(K) 150.0(1) Scanning mode Phi and omega scans θ maximum 27.48 “HKL” ranges −21 19; −23 22; −27 22 Reflections measured 41244 Unique data 21641 “Rint” 0.0174 Reflections used 14863 Criterion I > 2σI) Type of refinement Fsqd Hydrogen atoms Mixed Refined parameters 1025 Reflections/parameters 14 wR2 0.2107 R1 0.0656 Weights a, b 0.0961; 36.570 GoF 1.024 Difference peak/hole (e ÅP^(−3P)) 5.506(0.147)/−3.370(0.147) 

1. A borohydride metallocene complex of a lanthanide that corresponds to one or other of the following two formulae A and B:

where Ln represents the said lanthanide having an atomic number of between 57 and 71 inclusive, where, in the formula A, two identical or different ligand molecules Cp₁ and Cp2, each composed of a fluorenyl group which is substituted or unsubstituted, are connected to the lanthanide Ln, where, in the formula B, a ligand molecule composed of two identical or different fluorenyl groups Cp₁ and Cp₂ which are substituted or unsubstituted and which are connected to one another via a bridge P corresponding to the formula MR₁R₂, where M is an element from Group IVa of the Periodic Table of the Elements and where R₁ and R₂, which are identical or different, represent an alkyl group comprising from 1 to 20 carbon atoms, is connected to the lanthanide Ln, where L represents an alkali metal chosen from the group consisting of lithium, sodium and potassium, where N represents a molecule of a complexing solvent, such as an ether, where x is an integral or non-integral number which is greater than 0, and where p is an integer equal to 1 or
 2. 2. The complex according to claim 1, wherein L represents lithium.
 3. The complex according to claim 1, wherein N represents tetrahydrofuran.
 4. The complex according to claim 1, wherein x is equal to 1 and in that p is equal to 2, the complex being a dimer.
 5. The complex according to claim 1, wherein Cp₁ and Cp₂ are each composed of the same unsubstituted fluorenyl group which corresponds to the formula C₁₃H₉ or C₁₃H₈ for formula A or B respectively.
 6. The complex according to claim 1, wherein the complex corresponds to the formula B.
 7. The complex according to claim 6, wherein the element M included in the said bridge P of formula MR₁R₂ is silicon.
 8. The complex according to claim 7, wherein the complex corresponds to the formula:

where Flu represents an unsubstituted fluorenyl group of formula C₁₃H₈, where Me represents a methyl group, where Si is silicon, Nd is neodymium, Li is lithium and THF is tetrahydrofuran.
 9. The complex according to claim 7, wherein the complex corresponds to the formula:

where Flu represents an unsubstituted fluorenyl group of formula C₁₃H₈, where Me represents a methyl group, where Si is silicon, Nd is neodymium, Li is lithium and THF is tetrahydrofuran, where x is an integer ranging from 0 to
 3. 10. The complex according to claim 6, wherein the complex is in the form of single crystals.
 11. The complex according to claim 10, wherein the sad single crystals correspond to a monoclinic lattice system.
 12. The complex according to claim 10, wherein the single crystals correspond to a triclinic lattice system.
 13. A process for the preparation of a complex according to claim 1, wherein the process comprises reaction of a ligand salt of formula P—Cp₁Cp₂-L₂ and of a solution of lanthanide Ln tris(borohydride) dissolved in the complexing solvent and of formula Ln(BH₄)₃N₃.
 14. The process for the preparation of a complex according to claim 13, wherein the aid ligand salt corresponds to the formula Me₂SiFlu₂-Li₂ and in that the lanthanide tris(borohydride) corresponds to the formula Nd(BH₄)₃(THF)₃ where THF is tetrahydrofuran.
 15. The process for the preparation of a complex according to claim 13 or further comprising running, at ambient temperature, the ligand salt, dissolved in another solvent, such as diethyl ether, onto the solution of lanthanide tris(borohydride) in the form dissolved in this other solvent.
 16. A catalytic system which can be used for the copolymerization of at least one olefin and of at least one conjugated diene, comprising a metallocene complex of a lanthanide and a cocatalyst chosen from the group consisting of an alkylmagnesium, an alkyllithium, a Grignard reagent and a mixture of an alkyllithium and of an alkylaluminium, wherein said complex is a borohydride metallocene complex of a lanthanide as defined in claim
 1. 17. The catalytic system according to claim 16, wherein said cocatalyst is butyloctylmagnesium.
 18. A process for the copolymerization of olefins employing a catalytic system, the wherein the process comprises copolymerization of ethylene and butadiene using a catalytic system according to claim 17 in order to obtain a copolymer in which the units resulting from butadiene comprise links in the form of 1,2-cyclohexane.
 19. The copolymerization process according to claim 18, wherein the molar level of units resulting from butadiene in the copolymer is greater than 10%.
 20. The copolymerization process according to claim 18, wherein the molar level of the 1,2-cyclohexane links in the units of the copolymer which results from butadiene is equal to or greater than 20%.
 21. The copolymerization process according to claim 20, wherein the molar level of the 1,2-cyclohexane links in the units of said copolymer which result from butadiene is equal to or greater than 25%.
 22. A process for the copolymerization of olefins, comprising the copolymerization of ethylene and butadiene using the catalytic system according to claim 17 in order to obtain a copolymer in which the units resulting from butadiene comprise links in the form of 1,4-cyclohexane.
 23. A process for the copolymerization of olefins, wherein the process comprises copolymerization of ethylene and butadiene using the catalytic system according to claim 17 in order to obtain a copolymer in which the units resulting from butadiene comprise links in the form of 1,2-cyclohexane and 1,4-cyclohexane links.
 24. The copolymerization process according to claim 18, wherein the cocatalyst/complex molar ratio is chosen to be less than or equal to
 10. 25. The copolymerization process according to claim 24, wherein the cocatalyst/complex molar ratio is chosen to be less than or equal to
 5. 26. The copolymerization process according to claim 25, wherein the cocatalyst/complex molar ratio is chosen to be less than or equal to 2 and in that the polymerization is carried out under a pressure equal to or greater than 8 bar in order to obtain a number-average molecular weight Mn of the said copolymer which is equal to or greater than 200 000 g/mol.
 27. The copolymerization process according to claim 18, comprising: (i) a preliminary preparation of the catalytic system by reacting the complex with the said cocatalyst, then (ii) a reaction in suspension or in solution in a hydrocarbon solvent, such as toluene, and at a temperature of between −20° C. and 120° C. of the catalytic system obtained in (i) in the presence of the monomers to be polymerized.
 28. A copolymer of ethylene and butadiene that exhibits both: a molar level of units resulting from butadiene which is equal to or greater than 25%, and a molar level of 1,2-cyclohexane links in the said units resulting from butadiene which is equal to or greater than 25%.
 29. A copolymer of ethylene and butadiene according to claim 28, that exhibits a number-average molecular weight Mn equal to or greater than 30 000 g/mol.
 30. A copolymer of ethylene and butadiene obtained according to claim 22, that exhibits units resulting from butadiene comprising links in the form of 1,4-cyclohexane.
 31. A copolymer of ethylene and butadiene according to claim 30, that exhibits units resulting from butadiene in the form of 1,2-cyclohexane and 1,4-cyclohexane links. 